Erosion resistant coatings

ABSTRACT

An erosion resistant article such as rotor blades for helicopters and wind turbines having the leading edge surface protected from damage from high speed impingement of rain or sand with a protective coating formed from specific polyurethane or polyurea coating having a defined set of minimum physical properties where the protective coating can be applied as a liquid coating and cured in place or as a preformed complementary shaped covering to protect the leading edge against erosion damage in service.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.14/052,035, filed on Oct. 11, 2013, which is a divisional of U.S. patentapplication Ser. No. 12/815,963 filed Jun. 15, 2010, now issued as U.S.Pat. No. 8,557,388, which is a continuation of U.S. patent applicationSer. No. 11/136,827 filed on May 24, 2005, now issued as U.S. Pat. No.7,736,745, which claims the benefit of U.S. Provisional Application Ser.No. 60/573,819 filed May 24, 2004 and U.S. Provisional Application Ser.No. 60/649,443 filed Feb. 2, 2005, the entire contents of which arehereby incorporated by reference.

BACKGROUND

This disclosure relates to abrasion resistant coatings. Morespecifically, this disclosure relates to coatings that afford protectionagainst abrasion, wear, vibration, solid particle erosion and liquidparticle erosion.

Rain and sand erosion damage on leading edge surfaces of helicopterrotor blades, propeller blades, aircraft wings, radomes, and antenna arewell-known problems. Metallic coatings derived from metal such as, forexample, nickel, titanium, stainless steel, or the like, generallyprovide good resistance to erosion damage. These metallic coatings,however, have many disadvantages. They have poor sand erosion resistanceand may spark upon impact with sand particles. In addition, they reflectlight and radar signals, making them undesirable for militaryoperations.

In order to overcome problems with the metallic coatings, coatingscomprising polymers (polymeric coatings) have been used. The polymericcoatings are generally modified to have a low gloss by the incorporationof flatting agents. They are additionally modified by the incorporationof dyes and colorants to have a color similar to that of the rest of theaircraft, in order to minimize detection. These addition of the flattingagents and colorants to the coating reduces the ductility of thecoatings and makes them more susceptible to rain and/or sand erosion. Inparticular, the use of flatting agents to attain low gloss causes adecrease in the elongation to break and a substantial reduction in therain and/or sand erosion resistance.

In U.S. Pat. No. 4,110,317 to Moraveck, urethane coatings havingimproved weather and protective properties are provided by applying andcuring in an atmosphere containing moisture a coating compositioncomprising (1) an isocyanate-terminated prepolymer comprising of thereaction product of (a) a polytetramethylene ether glycol having anaverage molecular weight between about 500 and about 700, (b) anoxyalkylated triol having an average molecular weight between about 400and about 1000 in an amount between 0 and about 20 percent by weightbased on the combined weight of the oxyalkylated triol and thepolytetramethylene ether glycol, and (c) an organic diisocyanate and (2)an inert organic solvent. However, the percent elongation at break forthese compositions is not very high.

In military specification, MIL-C-85322B (2), titled “Coating,elastomeric, polyurethane, rain erosion”, published in 1999 by the NavalAir System Command, the specification calls for polyurethane coatingsbased on TDI-prepolymer and a ketimine or other amine type curing agent.The disclosed physical property requirements are a minimum tensilestrength of 1000 psi and a minimum elongation at break of 350% asdetermined by ASTM D2370. No mention of Shore A hardness or tensile setrecovery are disclosed. Chemglaze M331 and Aeroglaze M1433, bothmanufactured by Lord Corporation, are qualified under MIL-C-85322. Thecoatings are based on TDI prepolymer and a ketimine (methylenedianiline). There is no disclosure of physical properties in the M1433product datasheet. The M331 datasheet discloses that the physicalproperties of a cured M331 coating has a tensile strength of 350 kg/cm²,an elongation at break of 500% and a Shore A hardness of 95. Aeroglazeis available only in gloss gray color and Chemglaze only in gloss blackcolor. No low gloss versions are available to meet the demand of themodern military requirements.

In military specification, MIL-C-83231, titled “Coatings, polyurethane,rain protective for exterior aircraft and missile plastic parts”, issuedin 1969 and later replaced by SAE-AMS-C-83231 in 1999, thespecifications call for polyurethane coatings based on moisture ornon-moisture curing mechanism. There is no reference to the requirementsof physical properties in tensile strength, elongation at break, tensileset at break (recovery) and Shore A hardness. CAAPCOAT B-274 and AS-P108available from Caap Co. was approved under this specification.

CAAPCOAT B-274, available in black, is a polyurethane rain erosioncoating qualified under MIL-C-83231A, Type II, Class A, and CompositionL. According to its Materials Safety Datasheet (MSDS), it is based onmethylene bis(4-cyclohexylisocyante terminated polyester prepolymer. Thecuring agent is based on aliphatic amine. The accelerator is dibutyl tindilaurate. CAAPCOAT AS-P108 antistatic polyurethane rain erosion coatingis based on TDI-isocyanate terminated polytetramethylene glycolprepolymer. Its catalyst contains triethylene diamine and dipropyleneglycol.

In MIL-C-83445, titled “Coating system, polyurethane, non-yellowingwhite, rain protective, thermally reflective”, issued in 1974 and laterreplaced by SAE-AMS-C-85445 in 1999, the specification calls forpolyurethane coatings based on aliphatic or cycloaliphatic prepolymers.There is no reference to the requirements of physical properties intensile strength, elongation at break, tensile set at break (recovery)and Shore A hardness. The only commercial product qualified under thisspecification was Caapcoat C-W4. Its product datasheet discloses that ithas a minimum tensile strength of 210 kg/cm² and a minimum elongation ofat break of 350%. There is no disclosure of tensile set at break(recovery) and Shore A hardness. According to its MSDS, it is based onmethylene bis(4-cyclohexylisocyante terminated polyester prepolymer. Thecuring agent is an aliphatic amine. The accelerator is dibutyl tindilaurate.

The above three military standards do not specify the 85 degree glossrequirement, and hence the aforementioned coatings are supplied in highgloss black, gray or white. However, the present day militaryapplications specify low gloss sprayable coatings with an 85 degreegloss values of about 3 to about 5.

Erosion resistance coatings can generally include a base coat layer anda top coat layer. A widely used commercial polyurethane protectivecoating system in low gloss gray is CAAPCOAT FP®-250, which consists ofCAAPCOAT® FP-200, a high gloss polyurethane base coat and FP-050, whichis a lusterless polyurethane top coat. CAAPCOAT FP®-200 color matchedgloss polyurethane rain erosion coating is based on chemistry similar tothe C-W4. Its technical data sheet indicates that it has a minimumtensile strength at break of 210 kg/cm² and a minimum elongation atbreak of 350%. The FP-050, lusterless top coat, has a minimum tensilestrength of 315 kg/cm² and a minimum elongation at break of 300%.

None of the above sprayable coatings are satisfactory for today'smilitary applications as low gloss erosion protection coatings and thereis therefore a need for protective coatings that can meet present daymilitary specifications.

SUMMARY

A method of protecting a substrate against damage comprising disposingon a substrate one or more coatings, wherein one coating comprises anisocyanate-terminated polyurethane prepolymer and a curing agent;wherein the curing agents comprise polyaspartic esters, ketimines,aldimines, or a combination comprising at least one of the foregoingcuring agents; reacting the isocyanate-terminated polyurethaneprepolymer with a curing agent; wherein the reacting can optionally becarried out in the presence of moisture or heat; and curing theisocyanate-terminated polyurethane prepolymer to form the coating.

DETAILED DESCRIPTION

It is to be noted that as used herein, the terms “first,” “second,” andthe like do not denote any order or importance, but rather are used todistinguish one element from another, and the terms “the”, “a” and “an”do not denote a limitation of quantity, but rather denote the presenceof at least one of the referenced item. Furthermore, all rangesdisclosed herein are inclusive of the endpoints and independentlycombinable.

Disclosed herein are coating compositions and coatings that can beadvantageously used to provide resistance to abrasion, wear and erosionin a variety of substrates. The coating composition comprises an organicpolymer, a flatting agent and an optional solvent. An exemplary organicpolymer comprises a polyurethane elastomer and/or a polyurea elastomer.The coatings advantageously have an elongation of greater than or equalto about 350%, an 85 degree gloss of about 3 to about 5, and provideresistance against wear, abrasion, erosion, impact and vibration, or thelike, for a time period of greater than or equal to about 100 minutes.In one embodiment, the substrate can be coated by spray coating, dipcoating, brush coating, electrostatic painting, or the like. In anotherembodiment, the coating composition can be molded and affixed to thesubstrate to provide resistance against abrasion, wear and erosion.

The term coating composition refers to a fluid composition that issprayable or that can be brushed onto the substrate, or into which thesubstrate can be dipped. The term coating refers to a layer that isderived from the coating composition and is substantially free fromwater and/or solvent and that has undergone curing in an amounteffective to form an elastomer. A protective coating as defined as onethat is disposed directly or indirectly upon the substrate and cancomprise one or more layers, one of which is derived from the coatingcomposition. The term “disposed indirectly” refers to a coating that isseparated from the substrate by other layers, while the term “disposeddirectly” refers to layers that in intimate physical contact with thesubstrate.

In one exemplary embodiment, the protective coating can comprise a layerof primer, a base coat layer, an optional tie layer and a top coatlayer, wherein one of these layers is derived from the coatingcomposition and generally has a tensile strength of greater than orequal to about 1000 psi (70 kg/cm²), a tensile elongation at break ofgreater than or equal to about 350% for sprayable coatings, a tensileset at break of less than or equal to about 60%, a Shore A hardness ofabout 44 A to about 93 A and an optional 85 degree gloss value of about3 to about 5. In some embodiments, the base coat layer is optional,while in other embodiments, the top coat layer is optional.

The protective coating advantageously combines properties of hightensile strength with a high elongation at break and a low gloss (mattesurface finish). In one embodiment, the protective coating has a tensilestrength of greater than or equal to about 1000 psi (70 kg/cm²), atensile elongation at break of greater than or equal to about 350% forsprayable coatings, a tensile set at break of less than or equal toabout 60%, a Shore A hardness of about 44 A to about 93 A and an 85degree gloss value of about 3 to about 5. In another embodiment, thecoating can have a tensile elongation at break of greater than or equalto about 425%, preferably greater than or equal to about 600%,preferably greater than or equal to about 700%, and more preferablygreater than or equal to about 800%, while having a matte surfacefinish. As used herein the equivalent terms “matte” “flat” or“low-gloss” coating is as set out in ASTM D 523-89(1999) wherein a flatcoating is defined as a coating that registers gloss less than 15 on an85-degree meter or less than five on a 60-degree meter in accordancewith the ASTM method.

The resistance against wear, abrasion, erosion, impact and vibration isafforded even at very high velocities, impacts and rate of impact. Thecoating composition can therefore be advantageously used to coat theleading edge and foreword facing structures of vehicles, such as, forexample, aircraft wings, helicopter rotor blades, propeller blades, nosecones, radomes, fan blades, antennas, or the like, to protect them fromdamage due to rain, dust and/or sand. Vehicles as used herein refer toaircraft, automobiles, locomotives, ships, or the like. Otherapplications may include coatings for gold balls, mining equipment,railcar liners, stone impact protection coatings for motor vehicles,flexible adhesives, gap fillers, vibration and motion dampening, sounddampening, windshield crack filler, noise control, electronicencapsulation, glass lamination, textile coatings, leather coatings, andother areas in which the substrates are subjected to damage caused bywear, abrasion, erosion, impact and vibration, or the like.

Organic polymers that can be used in the coating composition as well asin the coating are thermoplastic polymers, thermosetting polymers, orblends and copolymers of thermoplastic polymers with thermosettingpolymers. Examples of suitable organic polymers are dendrimers,elastomers, ionic polymers, copolymers such as block copolymers, graftcopolymers, random copolymers, star block copolymers, or the like.Exemplary organic polymers are elastomers. An exemplary elastomercomprises polyurethane and/or a polyurea.

The organic polymers can comprise polyacetals, polyureas, polyurethanes,polyolefins, polyacrylics, polycarbonates, polyalkyds, polystyrenes,polyesters, polyamides, polyaramides, polyamideimides, polyarylates,polyarylsulfones, polyethersulfones, polyphenylene sulfides,polysulfones, polyimides, polyetherimides, polytetrafluoroethylenes,polyetherketones, polyether etherketones, polyether ketone ketones,polybenzoxazoles, polyoxadiazoles, polybenzothiazinophenothiazines,polybenzothiazoles, polypyrazinoquinoxalines, polypyromellitimides,polyquinoxalines, polybenzimidazoles, polyoxindoles,polyoxoisoindolines, polydioxoisoindolines, polytriazines,polypyridazines, polypiperazines, polypyridines, polypiperidines,polytriazoles, polypyrazoles, polycarboranes, polyoxabicyclononanes,polydibenzofurans, polyphthalides, polyacetals, polyanhydrides,polyvinyl ethers, polyvinyl thioethers, polyvinyl alcohols, polyvinylketones, polyvinyl halides, polyvinyl nitriles, polyvinyl esters,polysulfonates, polysulfides, polythioesters, polysulfones,polysulfonamides, polyureas, polyphosphazenes, polysilazanes,polyolefins, polysiloxanes, fluoropolymers, polybutadienes,polyisoprenes, or a combination comprising at least one of the foregoingorganic polymers. Exemplary organic polymers are polyurethanes and/orpolyureas. It is desirable for the polyurethane or the polyurea to be anelastomer. The aforementioned organic polymers listed above can beblended and/or copolymerized with the polyurethane or polyurea ifdesired.

The polyurethane elastomer comprises isocyanates having the generalformula:R(NCO)i  (I),wherein R is an organic radical having the valence of i, wherein i isgreater than or equal to about 2. R can be a substituted orunsubstituted hydrocarbon group (e.g., a methylene group or an arylenegroup).

The isocyanates can be aromatic or aliphatic. Useful aromaticdiisocyanates can include, for example, 2,4-toluene diisocyanate and2,6-toluene diisocyanate (each generally referred to as TDI); mixturesof the two TDI isomers; 4,4′-diisocyanatodiphenylmethane (MDI);p-phenylene diisocyanate (PPDI); diphenyl-4,4′-diisocyanate; dibenzyl-4,4′-diisocyanate; stilbene-4,4′-diisocyanate;benzophenone-4,4′-diisocyanate; 1,3- and 1,4-xylene diisocyanates; orthe like, or a combination comprising at least one of the foregoingaromatic isocyanates. Exemplary aromatic diisocyanates for thepreparation of polyurethane prepolymers include TDI, MDI, and PPDI.

Useful aliphatic diisocyanates can include, for example,1,6-hexamethylene diisocyanate (HDI); 1,3-cyclohexyl diisocyanate;1,4-cyclohexyl diisocyanate (CHDI); the saturated diphenylmethanediisocyanate known as H(12)MDI; (also known commercially asbis{4-isocyanatocyclohexyl}methane, 4,4′-methylene dicyclohexyldiisocyanate, 4,4-methylene bis (dicyclohexyl)diisocyanate, methylenedicyclohexyl diisocyanate, methylene bis (4-cyclohexylene isocyanate),saturated methylene diphenyl diisocyanate, and saturated methyl diphenyldiisocyanate), isophorone diisocyanate (IPDI); or the like; or acombination comprising at least one of the foregoing isocyanates. Anexemplary aliphatic diisocyanate is H(12)MDI.

Other exemplary polyisocyanates include hexamethylene diisocyanate(HDI), 2,2,4- and/or 2,4,4-trimethyl-1,6-hexamethylene diisocyanate,dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane,1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,4′-and/or 4,4′-diisocyanato-dicyclohexyl methane, 2,4- and/or4,4′-diisocyanato-diphenyl methane and mixtures of these isomers withtheir higher homologues which are obtained by the phosgenation ofaniline/formaldehyde condensates, 2,4- and/or 2,6-diisocyanatotolueneand any mixtures of these compounds.

In one embodiment, derivatives of these monomeric polyisocyanates can beused. These derivatives include polyisocyanates containing biuret groupsas described, for example, in U.S. Pat. Nos. 3,124,605, 3,201,372 andDE-OS 1,101,394; polyisocyanates containing isocyanurate groups asdescribed, for example, in U.S. Pat. No. 3,001,973, DE-PS 1,022,789,1,222,067 and 1,027,394 and DE-OS 1,929,034 and 2,004,048;polyisocyanates containing urethane groups as described, for example, inDE-OS 953,012, BE-PS 752,261 and U.S. Pat. Nos. 3,394,164 and 3,644,457;polyisocyanates containing carbodiimide groups as described in DE-PS1,092,007, U.S. Pat. No. 3,152,162 and DE-OS 2,504,400, 2,537,685 and2,552,350; and polyisocyanates containing allophanate groups asdescribed, for example, in GB-PS 994,890, BE-PS 761,626 and NL-OS7,102,524. In another embodiment,N,N′,N″-tris-(6-isocyanatohexyl)-biuret and mixtures thereof with itshigher homologues and N,N′,N″-tris-(6-isocyanatohexyl)-isocyanurate andmixtures thereof with its higher homologues containing more than oneisocyanurate ring can be used.

R in the formula (I) can also represent a polyurethane radical having avalence of i, in which case R(NCO)i is a composition known as anisocyanate-terminated polyurethane prepolymer or semi-prepolymer.Prepolymers or semi-prepolymers are formed when an excess of organicdiisocyanate monomer is reacted with an active hydrogen containingcomponent.

In one embodiment, the active hydrogen containing component is a polyol.In one embodiment, the prepolymers and semi-prepolymers may suitably beprepared from low molecular weight polyol compounds having a molecularweight of 62 to 299. The polyols can also have a molecular weight ofabout 300 to about 20,000, preferably about 500 to about 10,000, morepreferably about 1000 to 5000, as determined from the functionality andthe OH number. In one embodiment, the polyols can have at least twohydroxyl groups per molecule and generally have a hydroxyl group contentof about 0.5 to 17 wt %, preferably about 1 to 5 wt %.

Examples of suitable polyols are polyester polyols, polycaprolactonepolyols, polyether polyols, polyhydroxy polycarbonates, polyhydroxypolyacetals, polyhydroxy polyacrylates, polyhydroxy polyester amides andpolyhydroxy polythioethers. Exemplary polyols are polyester polyols,polyether polyols, polyesters derived from lactones (e.g.,ε-caprolactone or ω-hydroxycaproic acid), or a combination comprising atleast one of the foregoing polyols.

Suitable polyester polyols include reaction products of polyhydric ordihydric alcohols with polybasic or preferably dibasic carboxylic acids.Instead of these polycarboxylic acids, the corresponding carboxylic acidanhydrides or polycarboxylic acid esters of lower alcohols or mixturesthereof may be used for preparing the polyester polyols. Thepolycarboxylic acids may be aliphatic, cycloaliphatic, aromatic and/orheterocyclic and they may be substituted (e.g., by halogen atoms),and/or unsaturated. Examples include succinic acid, adipic acid, subericacid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid,terephthalic acid, trimellitic acid, phthalic acid anhydride,tetrahydrophthalic acid anhydride, hexahydrophthalic acid anhydride,tetrachlorophthalic acid anhydride, endomethylene tetrahydrophthalicacid anhydride, glutaric acid anhydride, maleic acid, maleic acidanhydride, fumaric acid, dimeric and trimeric fatty acids such as oleicacid, which may be mixed with monomeric fatty acids, dimethylterephthalates, bis-glycol terephthalate, or the like, or a combinationcomprising at least one of the foregoing. Polyesters of lactones, e.g.ε-caprolactone or hydroxy-carboxylic acids, e.g. ω-hydroxycaproic acid,may also be used.

The polyether polyols are obtained by the chemical addition of alkyleneoxides, such as, for example, ethylene oxide, propylene oxide andmixtures thereof, to water or polyhydric alcohols, such as, for example,ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butyleneglycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentylglycol, cyclohexane dimethanol (1,4-bis-hydroxymethylcyclohexane),2-methyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, triethyleneglycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol,polypropylene glycol, polytetramethylene glycol, dibutylene glycol andpolybutylene glycol, glycerine, trimethylolpropane, or the like, or acombination comprising at least one of the foregoing polyhydricalcohols.

Examples of suitable starting molecules for the polyether polyolsinclude monomeric polyols, water, organic polyamines having at least twoNH bonds and mixtures of these starting molecules. Ethylene oxide and/orpropylene oxide are particularly suitable alkylene oxides for thealkoxylation reaction. These alkylene oxides may be introduced into thealkoxylation reaction in any sequence or as a mixture.

Suitable polyhydroxy polycarbonates include those obtained by reactingdiols, such as, for example, 1,3-propanediol, 1,4-butanediol and/or1,6-hexanediol, diethylene glycol, triethylene glycol or tetraethyleneglycol with diarylcarbonates or cyclic carbonates. The reaction betweenthe diols and the diarylcarbonates or the cyclic carbonates takes placein the presence of phosgene. Also suitable are polyester carbonatesobtained by reacting the previously described polyesters or polylactoneswith phosgene, diaryl carbonates or cyclic carbonates.

The prepolymers generally have an isocyanate content of about 0.5 toabout 40 weight percent (wt %), based on the weight of the prepolymerafter reaction. In one embodiment, the prepolymers generally have anisocyanate content of about 1 to about 20 wt %, based on the weight ofthe prepolymer after reaction. The prepolymer is generally manufacturedusing starting materials at an NCO/OH equivalent ratio of about 1.05:1to about 10:1, preferably about 1.1:1 to about 3:1. The reaction isoptionally followed by the distillative removal of any unreactedvolatile starting polyisocyanates still present.

Exemplary isocyanate prepolymers are TDI-ether, TDI-ester, TDI-lactone,MDI-ether, MDI-ester, H12MDI-ether, H12MDI-ester and similar prepolymersmade from HDI, IPDI and PPDI. The isocyanate prepolymers with low freeisocyanate monomers are preferred. Although the examples presentisocyanate-terminated prepolymers based on TDI and H12MDI, it isexpected that other prepolymers and curing agents can be used toformulate the highly rain protective coating having tensile strength ofgreater than 70 kg/cm², elongation at break of higher than 350%, andtensile set value of less than 150%, as defined in this specification.Examples of suitable prepolymers are available from Air Products,Uniroyal, Bayer, Anderson Development and other polyurethane rawmaterial suppliers.

In general, those prepolymers that are useful in forming polyurethaneelastomers with MOCA (4,4′-methylenebis (orthochloroaniline) (MBCA) canbe used. Those prepolymers that produce elastomers of 40 A-75 D withMOCA, or polyols can be used.

Examples of suitable commercially available prepolymers are AIRTHANE®series, VERSATHANE®, ADIPRENE® and VIBRATHANE® prepolymers, all of whichare commercially available from Air Products. Especially preferred arethose with very low free isocyanate monomers, such as AIRTHANE® PETseries, ADIPRENE® LF-SERIES and VERSATHANE®. Examples of preferredprepolymers are: AIRTHANE® PEP-70A, PHP-70A, PET-80A, PET-85A, PET-90A,PET-91A, PET-93A, PET-95A, AIRTHANE® PET-60D, AIRTHANE® PHP-70D,AIRTHANE® PET-70D. VERSATHANE® A-7QM, VERSATHANE® A-75QMSP, VERSATHANE®A-8QM, VERSATHANE® A-85QM, VERSATHANE® A-8, VERSATHANE® A-85L,VERSATHANE® A-9, VERSATHANE® A-9QM, VERSATHANE® D-5QM, VERSATHANE®D-5QM, VERSATHANE® D-55, VERSATHANE® D-7, VERSATHANE®-C 2070,VERSATHANE®-C 1080, VERSATHANE®-C 1090, VERSATHANE®-C 1050,VERSATHANE®-C 1160, AIRTHANE® PST-70A, PST-80A, PST-85A, PST-90A, andPST-95A.

Other examples of suitable prepolymers are ADIPRENE® and VIBRATHANE®isocyanate terminated prepolymers supplied by Uniroyal Chemical Company.For example, VIBRATHANE® 6060 TDI-polylactone, ADIPRENE® LW-520(H12MDI), LW-570 (H12MDI), ADIPRENE® HDI Prepolymer LFH 1570, LFH120,LFH710, ADIPRENE® PPDI-prepolymers LFP1950A (ester), LFP2950A (lactone),LFP590D (ether), LFP850A (ether), LFP950A (ether). Other VIBRATHANES®and ADIPRENE® extreme grades may also be used.

Other useful commercially available aromatic and aliphatic prepolymersare BAYTEC® WE-180 (Isocyanate-terminated PTMEG prepolymer based onHMDI, 18% isocyanate (NCO)) and BAYTEC® WP-260 (Isocyanate-terminatedPPG Polyether prepolymer based on HMDI, 26% NCO).

Other aliphatic prepolymers available from Anderson Development Companyinclude ANDUR® AL80-5AP/FP, AL80-5AP, and AL-80-5AP.

The prepolymers are generally present in the coating composition in anamount of about 10 wt % to about 95 wt %, based on the total weight ofthe coating composition. An exemplary amount of prepolymer is about 20to 70 wt %, based on the total weight of the coating composition.

The coating composition also comprises an optional curing agent.Examples of suitable curing agents are polyaspartic esters, aldimines,ketimines, amines, polyols, or the like, or a combination comprising atleast one of the foregoing curing agents. In one embodiment, suitablediamines can be converted into corresponding aldimine or ketimines foruse in sprayable coating compositions. In another embodiment, aldiminesor ketimines and polyaspartic esters can be beneficially combined in thesame coating formulation to provide improved properties. Amines may alsobe combined with the aldimines, ketimes, or the polyaspartic esterstogether to form the curing agents. Examples of suitable aspartic estersare those as disclosed in U.S. Pat. Nos. 5,126,170 and 5,236,741,incorporated herein by reference in their entireties. Other asparticesters may be used as long as the combination with the prepolymerproduce the high tensile, high elongation and low tensile set.

The polyaspartic ester has the general formula (II):R¹O₂CCH₂CH(CO₂R²)NH—R₅—NHCH(CO₂R³)CH₂CO₂R⁴  (II),wherein R¹, R², R³, and R⁴ are the same or different and each are alkylgroups having an amount of about 1 to about 12 carbon atoms. In oneembodiment, the alkyl groups have an amount of 1 to about 4 carbonatoms. An exemplary alkyl group is an ethyl group. R₅ can be aliphatic,alicyclic, or aromatic.

An exemplary polyaspartic ester is shown in formula (III):

wherein R₅ can have the structures shown in formulas (IV)-(VII) below:

wherein Me represents a methyl group.

Examples of suitable polyaspartic esters are DESMOPHEN® NH1220, NH1420,NH1521, NH1520, or PAC XP2528. Other polyaspartic esters and ketimines,such as DESMOPHEN® LS2965A, may also be used as long as thesecombinations with the prepolymer produce an elastomer having a highelongation at break and low tensile set.

Although polyaspartic esters have been marketed commercially for usewith aliphatic polyisocyanates, it has been discovered that they arealso suitable for use with TDI and/or MH12DI based prepolymers.

Examples of suitable aromatic amines that can be used as curing agentsare phenylene diamine, 4,4′methylene-bis-(2-chloroaniline),4,4′methylenedianiline (MDA), 4,4′methylenebis(2,6-diethylaniline),4,4′methylenebis(2,6-dimethylaniline),4,4′methylenebis(2-isopropyl-6-methylaniline),4,4′methylenebis(2ethyl-6-methylaniline), 4,4′methylenebis(2,6-isopropylaniline),4,4′methylenebis(3-chloro-2,6-diethylaniline) (MCDEA),1,3-propanediolbis(4-aminobenzoate), diethyltoluenediamine (DETDA),dimethylthiotoluenediamine; or the like; or a combination comprising atleast one of the foregoing aromatic amines.

Examples of commercially available aromatic amines such as ETHACURE®100, ETHACURE® 300, CLEAR LINK® series amines, VERSLINK® series amines.JAFFAMINE® series amines, VIBRACURE® series curatives, and UNILINK®series amines, or the like. In one embodiment, cyclic and aromaticpolyols can be used to simulate an aromatic amine in forming a hardsegment (rigid phase) in the polyurethane. Long chain polyols can beused like long chain polyamines to form the soft segments.

When polyaspartic esters are used as the curing agent, an optionalco-curing agent can be used. Aldimines, ketimines, aromatic diamines anddiols can be used as co-curing agents. Aldimines curing agents can beprepared from polyamines having cyclic groups. Aldimines used as curingagents have structures corresponding to the formula (VIII):X₁—[N═CHCH)(R₆)(R₇)]n  (VIII),wherein X₁ represents an organic group that has a valency of n and isobtained by removing the amino groups from a cyclic organic polyaminehaving (cyclo)aliphatically-bound amino groups, preferably a diamine andmore preferably a hydrocarbon group obtained by removing the aminogroups from a diamine having at least one cycloaliphatically-bound aminogroup, R₆ and R₇ may be the same or different and represent organicgroups which are inert towards isocyanate groups at a temperature of100° C., or less, preferably containing 1 to 10, more preferably 1 to 6,carbon atoms, or R₆ and R₇ together with the β-carbon atom form acycloaliphatic or heterocyclic ring and n represents an integer having avalue of at least 2, preferably 2 to 6, more preferably 2 to 4 and mostpreferably 2.

Aldimine are generally preferred over ketimines for the longer pot lifein sprayable coatings. Examples of suitable aldimines are latentaliphatic polyamines. Examples of commercially available aldimines areDESMOPHEN® PAC XP7076 and PAC XP7068. Other exemplary materials includeDESMOPHEN® PAC XP7109, XP7083, and XP7069. Especially preferred areisophoronediamine aldimines (IPDA aldimines).

In one embodiment, the curing agent can comprise polyaspartic esters,ketimines, aldimines, or a combination comprising at least one of theforegoing curing agents. Examples of combinations of curing agents arepolyaspartic esters with aldimines, polyaspartic esters with ketiminesor aldimines with ketimines. The aldimine and polyaspartic ester of thisinvention can be used with any isocyanate-terminated prepolymers. In oneembodiment, the aldimines and polyaspartic esters function as MOCAreplacement for polyurethane/polyurea elastomers. The relative ratios ofthe prepolymer/curing agent that form the high elongation elastomers canbe easily found by doing a series of trial formulations with variousprepolymer-curing agent ratios. The optimum ratios depend on thechemical structures of the prepolymers and the curing agents, as apolyurethane elastomer is formed with rigid blocks and soft blocks.Rigid (cyclic) prepolymers can be paired with soft (linear) curingagents or vice versa. Cyclic curing agents and linear curing agents canbe used. Examples of cyclic curing agents are aromatic diamines andcycloaliphatic diamines. Combination of di-, tri- or tetra functionalcuring agents may be used as long as the resulting physical propertiesdo not deviate far from the desired values.

While this disclosure relates curable compositions based onisocyanate-terminated prepolymers, a person skilled in the art maydesign a curable resin system by shifting some of the polyols in theprepolymer into the curing agent side, and form an end product withsimilar properties to those with pre-reacted prepolymers.

As the aldimine and polyaspartic esters permit one of ordinary skill inthe art to investigate the relationship of the physical properties ofthe coatings to their potential erosion resistance behaviors, a goodoverall correlation evolved after testing numerous compositions. Theoverall correlation is the subject of this invention. This correlationextends beyond the isocyanate-aldimine and polyaspartic chemistry. Thesame pattern exists with aqueous polyurethane dispersions that have beenpolymerized. Additional curing agent can be added, but can also beeliminated. The same pattern also exists with solid polyurethaneelastomers.

If desired, the reaction between the prepolymer and the curative agentto form the polyurethane can take place in the presence of a catalyst.Examples of suitable catalysts include organometallic compounds, such asorganotins, (e.g., dibutyltindilaurate, stannous octoate, or the like);tertiary amines, (e.g., triethylenediamine, triethylamine,n-ethylmorpholine, dimethylcyclohexylamine,1,8-diazabicyclo-5,4,0-undecene-7, or the like), or a combinationcomprising at least one of the foregoing catalysts.

In one embodiment, the curing agent can be a multifunctional imine. Themulti-functional imine may be represented by the formula (IX):

wherein R₈, R₉, R₁₀, and R₁₁ are radicals that can be the same ordifferent and wherein each is independently selected from the groupconsisting of hydrogen, an alkyl having from 1 to 10 carbon atoms andphenyl and wherein A may be any radical having a molecular weight from26 to 7000.

In an exemplary embodiment, the multi-functional imine is a ketimineformed by the reaction of a primary di- or triamine with a ketone. Thecuring agent can be prepared by refluxing the primary amine and ketoneor aldehyde together in the presence of an azeotroping agent such asbenzene, toluene or xylene. Examples of suitable curing agents that areuseful in the coating composition are 1,2-ethylene bis(isopentylideneimine), 1,2-hexylene bis(isopentylidene imine), 1,2-propylenebis(isopentylidene imine), p,p′-bisphenylene bis(isopentylidene imine),1,2-ethylene bis(isopropylidene imine), 1,3-propylene bis(isopropylideneimine, p-phenylene bis(isopentylidene imine), m-phenylenebis(isopropylidene imine), 1, 5-naphthylene bis(isopropylidene imine),or the like, or a combination comprising at least one of the foregoingimine curing agents.

In one embodiment, the isocyanate-terminated polyurethane prepolymer canbe reacted with a ketimine or polyketimine to form ketiminefunctionalized polyurethane prepolymers. The ketimine functionalizedpolyurethane is then alkylated to form a crosslinked polyurethane. Inaddition to the aforementioned amines, low unsaturation polyols such asACCLAIM® polyols or polyamines derived from ACCLAIM® polyols can beadvantageously used.

In one embodiment, a curing agent is not used to effect thecrosslinking. In this event, atmospheric moisture may serve to catalyzethe reaction between the polyurethane and the curing agent. This isreferred to as moisture cure. In another embodiment, the moisture curecan be used when the coating composition comprises curing agents such aspolyaspartic esters, ketimines, aldimines, or a combination comprisingat least one of the foregoing curing agents. The coating compositioncomprising the curing agents is exposed to moisture to facilitate thecrosslinking reaction.

Flatting agents are added to lower the gloss of the coating surface. Theflatting agent migrates to the surface of the coating as the coating isdried. This produces a rough surface that randomly scatters reflectedlight, which creates a matte surface finish (low gloss finish).Important considerations for selection of a flatting agent are particlesize distribution, rheological effects, color/clarity, and ease ofdispersion and good suspension in coating solution.

Examples of suitable flatting agents are fine particle powders oforganic and inorganic materials, urea-formaldehydes, silicas such as,for example, precipitated silica and fumed silica, polymeric beads,talc, alumina, calcium carbonate, or the like, or a combinationcomprising at least one of the foregoing flatting agents. An exemplaryflatting agent is silica. Examples of suitable silica flatting agentsare “LO-VEL® 27” and “LO-VEL® 275” (ultrafine amorphous silica)commercially available from PPG Industries, Inc., Pittsburgh, Pa. andACEMATT® TS-100 from Degussa.

It is desirable for the flatting agents to have average particle sizesof about 1 to about 20 micrometers. In one embodiment, the flattingagent has an average particle size of 2 to about 15 micrometers. Inanother embodiment, the flatting agent has an average particle size of 3to about 12 micrometers.

The flatting agent is added to the coating composition in an amount ofup to about 20 wt %, based on the total weight of the coatingcomposition. In one embodiment, the flatting agent is added to thecoating composition in an amount of about 1 to about 15 wt %, based onthe total weight of the coating composition. In another embodiment, theflatting agent is added to the coating composition in an amount of about2 to about 10 wt %, based on the total weight of the coatingcomposition. In another embodiment, the flatting agent is added to thecoating composition in an amount of about 3 to about 7 wt %, based onthe total weight of the coating composition.

The coating composition also comprises an optional solvent. Solvents caninclude water and/or an organic solvent. Organic solvents may be proticsolvents, aprotic solvents, or mixtures comprising at least one of theforegoing solvents. Examples of suitable organic solvents are toluene,xylene, butyl acetate, propyl acetate, methyl isobutyl ketone, methyln-amyl ketone (MAK), methoxypropyl acetate, N-methyl pyrrolidone, or acombination comprising at least one of the foregoing solvents. When thesolvent substantially comprises water, then the coating composition andthe coating obtained from the coating composition is referred to asbeing an aqueous coating composition and an aqueous coatingrespectively. When the solvent substantially comprises an organicsolvent, then the coating composition and the coating is referred to asbeing a non-aqueous coating composition and a non-aqueous coatingrespectively.

Coating compositions can also be substantially solvent free. In thosesituations where the coating composition has a low enough viscosity(without the use of solvent or water), solvents (including water) maynot be added to the coating composition and the coating composition isreferred to as being 100% solids based.

When solvent is added to the coating composition, it is generally addedin an amount of about 20 to about 60 wt %, based on the total weight ofthe coating composition. In one embodiment, the solvent is added to thecoating composition in an amount of about 25 to about 55 wt %, based onthe total weight of the coating composition. In another embodiment, thesolvent is added to the coating composition in an amount of about 35 toabout 50 wt %, based on the total weight of the coating composition. Inyet another embodiment, the solvent is added to the coating compositionin an amount of about 40 to about 45 wt %, based on the total weight ofthe coating composition.

For aqueous coatings, polyurethane dispersions can be used with orwithout curing agents. These polyurethane dispersions are generallycommerically available. The polyurethane dispersions are pre-reactedpolyurethanes polymers and may have free carboxyl, hydroxyl or otherreactive functional groups for further crosslinking. The crosslinking ofaqueous polyurethane dispersions may be accomplished by the use ofisocyanates, epoxy, or aziridines functional materials. Different gradesof aqueous polyurethane dispersions may be blended together to achievethe desired properties. The polyurethane dispersions may be used aloneor in combination with the non-aqueous (solvent based) protectivecoatings.

For example, aqueous coatings may be used as the base coat and thenonaqueous coatings used as the top coat, or vice versa. In anothermethod, alternating layers or any random combination of the aqueous andnon-aqueous coatings may be sprayed sequentially to form the protectivecoating. This is possible because the moisture triggers the curing ofaldimine or ketimine containing coatings and moisture also catalyzes thecuring of polyaspartic ester cured coatings. In other words, themoisture present in an aqueous coating can facilitate the crosslinkingreaction in an adjacent non-aqueous coating.

Other additives useful in the coating compositions include levelingagents, defoamers, hydrolysis stabilizers, UV stabilizers, pigments,dispersants, curing accelerators, diluents, or combinations thereof.

In one embodiment, fillers that impart electrical conductivity orthermal (heat) conductivity can be added to the coating composition.Examples of suitable heat conductive fillers are metal powders, metalflakes, metal fibers, milled metal fibers, alumina, graphite, boronnitride, aluminum nitride, surface treated or coated aluminum nitrides,silica coated aluminum nitride, carbon nanotubes, carbon fibers andmilled carbon fibers, silicone carbide, or the like, or a combinationcomprising at least one of the foregoing additives.

Examples of suitable electrically conductive fillers are metal powders,metal flakes, metal fibers, milled metal fibers, metal-coated syntheticfibers, metal-coated glass spheres, metal-coated hollow spheres,graphite, carbon nanotubes, vapor grown carbon fibers, carbon fibers andmilled carbon fibers, carbon coated synthetic fibers, buckyballs,electroactive polymers, antimony-doped tin oxide, conductive metaloxides such as indium tin oxide, tertiary ammonium salt compounds,carbon blacks, coke, or the like, or a combination comprising at leastone of the foregoing electrically conductive fillers.

These fillers can be added to the coating composition at concentrationseffective to obtain desired properties. Other fillers that can be usedto control dielectric constants are well known. Examples include variousmetal oxides, metal powders, metal fibers, micro-balloons, or the like,or a combination comprising at least one of the foregoing fillers.

Other fillers that are used to control the interaction of the coatingwith electromagnetic radiation involved in radar devices, infrareddetection devices can also be added to the base elastomers of thisinvention.

The coating composition can be applied in one or more layers to thesubstrate in order to create a protective coating. The coatingcomposition can be applied by spraying, brush coating, immersion,flooding, by means of rollers, by using doctor applicators, or acombination comprising at least one of the foregoing processes. Theseprocesses are suitable for the formation of a protective coating onvarious substrates, e.g., metals, plastics, wood, cement, concrete orglass. It is desirable to apply one or more layers having a tensilestrength of greater than or equal to about 1000 psi (70 kg/cm²), atensile elongation at break of greater than or equal to about 350%, atensile set at break of less than or equal to about 60%, a Shore Ahardness of about 44 A to about 93 A and an optional 85 degree glossvalue of less than or equal to about 10, preferably about 3 to about 5.

The surface of the substrate to be coated with the coating compositionmay optionally be treated (i.e., cleaned) to improve adhesion to thesubstrate. The substrate may also optionally be treated by coating itwith a layer of primer, a base coat layer, a tie layer and a top coatlayer if desired. In one embodiment, the primer, the base coat layer aswell as the top coat layer can all be derived from the coatingcomposition. In another embodiment, only the top coat layer can bederived from the coating composition.

After the application of the optional primer and the base coat, thecoating composition may be applied to the substrate to form a coatingthat offers a high resistance to impact, wear, abrasion and/orvibration. The coating can be applied in a single step or in multiplesteps and can exist in the form of a single layer or multiple layers.The protective coating can therefore consist of a single layer of thecoating composition applied to the substrate. Alternatively, theprotective coating can comprise multiple layers, wherein one of thelayers comprises a coating that is derived from the coating composition.

As discussed above, the substrate may optionally be treated prior to theapplication of the coating. The treatment is conducted for purposes ofcleaning the surface of the substrate and for purposes of improvingadhesion between the coating and the substrate. Treating the surface mayinvolve mechanical roughening, grit blasting, sanding, cleaning,chemical etching, plasma treatment, chemical conversion coating, orother processes known to improve the adhesion to the substrate ofprimers or coatings applied later in the process.

As discussed above, treatment of the substrate may be followed by theapplication of an optional layer of primer and/or a top coat layer tothe substrate. A primer is generally applied for corrosion protection,or to enhance the removal of the top coat layer when the substrate is tobe refurbished. Examples of suitable corrosion resistant primers areepoxy and polyurethane coatings containing corrosion inhibitors. Washprimers comprising polyvinyl butyral chemistry are also used. The washprimers can assist the removal of the protective materials because oftheir solubility in solvents. An exemplary primer is a water borne epoxyprimer because it permits the application of a top coat within one hourof its application. It also permits the application of a protectivecoating in less than or equal to about 8 hours of the application of theprimer. The use of the water borne epoxy primer thus permits animprovement in speed of application and allows for productivityimprovements over other commercially available primers.

When the layer of primer is applied to the substrate it generally has athickness of about 0.5 to about 2.0 mils. A preferred thickness for thelayer of primer is about 0.6 to about 1.2 mils.

The substrate having the layer of primer is then coated with an optionalbase coat layer. The base coat layer is applied within a limited timewindow, so as to facilitate optimum adhesion to the layer of primer. Thetime to spray varies with each primer formulation, as instructed by themanufacturers. For the exemplary water-borne epoxy primers, the basecoats can be sprayed within about 1 to about 3 hours after the primer issprayed. The base coat layer was dried at ambient temperature. The basecoat layer can also be derived from the coating composition. In oneembodiment, the coating composition for the base coat layer does notutilize flatting agents. It is desirable for the base coat layer to havea tensile strength of greater than or equal to about 1000 psi (70kg/cm²), a tensile elongation at break of greater than or equal to about350%, a tensile set at break of less than or equal to about 60%, and aShore A hardness of about 44 A to about 93 A. The base coat layer can bea high gloss, semi-gloss layer, low gloss or matte layer.

If the base coat layer and the layer of primer do not have suitableadhesion to each other, another tiecoat layer may be applied between thelayer of primer and the base coat layer. For example, polyurethane basecoat layer based on H12MDI has lower adhesion to a layer of epoxyprimer. An example of a suitable tiecoat layer is an aqueouspolyurethane layer or a TDI-based polyurethane layer. Other coatings maybe used as long as they improve the adhesion between the layer primerand the base coat layer.

The coating composition comprising flatting agents may then be coatedonto the base coat layer to form the top coat layer. As discussed above,the coating composition may be applied in a single layer or in multiplelayers. In other words, the protective coating can comprise multiplelayers, one of which has a tensile strength of greater than or equal toabout 1000 psi (70 kg/cm²), a tensile elongation at break of greaterthan or equal to about 350% for sprayable coatings, a tensile set atbreak of less than or equal to about 60%, a Shore A hardness of about 44A to about 93 A and an 85 degree gloss value of less than or equal toabout 10, preferably about 3 to about 5.

As noted above, the coating composition may be applied to the substratein a plurality of layers to form the coating. In one embodiment, thecoating composition may be applied in an amount of up to seven layers.In another embodiment, the coating composition may be applied in anamount of up to six layers. In another embodiment, the coatingcomposition may be applied in an amount of up to five layers. In anotherembodiment, the coating composition may be applied in an amount of up tofour layers. In another embodiment, the coating composition may beapplied in an amount of up to three layers. In yet another embodiment,the coating composition may be applied in an amount of up to two layers.These layers can have the same or different compositions.

As noted above, the coating can be formed from the coating compositionin a variety of ways. In one embodiment, the coating can be formed byspraying, dipping, solution coating of the substrate. In anotherembodiment, a preformed sheet produced by spraying, dipping or solutioncoating of the coating composition is first prepared. The preformedsheet is then adhesively bonded to the substrate to afford resistance toerosion, wear and abrasion. In yet another embodiment, the coatingcomposition can be molded to form a layer. The layer is then adhesivelybonded to the substrate to form the protective coating. The molding canbe accomplished through injection molding, compression molding, vacuumforming, blow molding, or the like. An exemplary method of forming theprotective coating is by spraying the coating composition onto thesubstrate.

In one embodiment, after the application of the coating composition tothe substrate, it can be cured by moisture curing and/or heat curing. Ifsolvent is present in the coating composition, it is desirable to driveoff substantially all of the moisture during the curing process. Thecoatings may be cured at either ambient temperature (e.g., by air dryingor so-called forced drying), or at an elevated temperature (heatcuring). A heat curing process to effect curing and to drive off thesolvent can utilize heat from convection, conduction and/or radiation.Electromagnetic radiation in the form of microwave radiation, infraredradiation and/or ultraviolet radiation can be used to facilitate curing.

In the spraying process, coating compositions having different amountsand/or types of solvent can be used to form the coating layers on thesubstrate. For example, aqueous coatings can be used sequentially withnon-aqueous coatings, especially when the non-aqueous coatings use themoisture curing mechanism. In this case, aqueous coating compositionscan be used to apply the layer of primer and the tiecoat layer, whilenon-aqueous coating compositions can be used for an intermediate coat orfinal top coat layer. In another embodiment, the aqueous coatingcompositions can be used to form all of the protective coating layers(e.g., the layer of primer, base coat layer, tie layer, or the like)other than the top coat layer, while a non-aqueous coating compositionis used as the final top coat.

In another method of using the coating composition, alternating layersor any random combination of the aqueous and non-aqueous coatingcompositions may be sprayed in any sequence to form the protectivecoating. This is possible because the moisture triggers the curing ofpolyurethane with aldimine or ketimine curing agents and moisture alsocatalyze the curing of polyaspartic ester cured coatings. The combineduse of aqueous and non-aqueous sprayable coating compositions provides amethod of reducing the overall water sensitivity of aqueous coatings,while reducing the amount of organic solvents used to form theprotective coating.

As detailed above, it is desirable to have low gloss films for militaryapplications. In one embodiment, in order to form a low gloss coating,three approaches can be used: 1) a coating composition that produces acoating having a matte (low gloss) surface can be used to coat theentire substrate. In this case, the entire thickness of the coating isobtained from a single coating composition; 2) coating compositions thatform alternating high gloss and semigloss surfaces are used as basecoats to form the bulk of the total protective coating thickness and acoating composition that produces a coating having a matte surface isused as a top coat layer to finish the visible surface; and 3) coatingcompositions that form high gloss and semigloss surfaces and coatingcompositions that produce matte surface finishes are used sequentiallyor randomly while the coating composition that produces the matte finishcoating is used as a top coat layer to finish the visible surface.

In one embodiment, it is desirable to obtain maximum effect from theflatting agents present in the coating composition in order to produce amatte surface finish. In order to produce a matte surface finish, thelast layer of the coating (e.g., top coat layer) having a matte surfaceneeds to be sprayed after the base coat has cured to a solid state and asubstantial amount of the solvents in the underlying layers hasevaporated. When the top coat layer coating having the matte finish issprayed too early (i.e., before substantial solvent evaporation hasoccurred), the flatting agents in the top coat layer may get absorbedinto the underlying layers base coat and a higher gloss appearanceresults.

In general, protective sprayable coatings are used at a thickness ofabout 0.014″ for leading edge protection of an aircraft. In order toachieve higher rain erosion resistance and reach the required thicknessin reasonable amount of time, a higher solid gloss base coat is used tobuild up to the 0.012-0.013″ thickness, and then followed by0.001-0.002″ of a low luster matte top coat.

In addition, there is a possibility of cracking in the top coat layer.These cracking patterns are due to the difference in the rate ofshrinkage between the glossy base coat layer and top coat layer havingthe matte surface finish. In order to prevent such cracking, it isgenerally desirable for the underlying layers (i.e., the base coatlayer) to be allowed to dry for a time period of about 1 to bout 4 hoursbefore any additional coating composition is applied. The time periodneeded depends on the curing speed of the underlying layers and theambient room temperature and humidity. The top coat layer having thematte surface finish should preferably be sprayed before the base coatlayer is completely cured. Lower adhesion between the base coat layerand the top coat layer may result if the base coat layer is fully curedprior to the application of the top coat layer. The top coat layers aregenerally applied after a time period of about 1.5 to about 3 hoursafter the application of the base coat layer.

In another possible method of forming the protective coating, sprayablecoatings may be sprayed over a releasable structure (tooling) of similardimension and configuration as the substrate that is to be coated.Depending on the releasable structure, the sprayable coatings can beconverted into boots, sheet, films, or tapes (called “cured forms” forthis purpose). After drying and curing, the “cured forms” can be removedand used later on the substrate of similar dimensions and configuration.Adhesive can be used to bond the “cured forms”. The sprayable coatingsmay be sprayed over the “cured form” if desired. While the coatings arestill wet, the precured “form” can be bonded to the substrate using theprotective coating as an adhesive. This method of affixing theprotective coating saves the time and expense for field repair depots.Other adhesives may also be used.

For protective materials preformed into boots, films, sheets and tapes,the erosion protection layers can also be formed by adhesive bondingonto the substrate. The molded boots, films or sheets can be bonded tothe substrate with the use of liquid primers and adhesives, or they canbe precoated with a pressure sensitive adhesive or other dry adhesives.The adhesive is activated upon contact. In other processes, Part A of atwo-part reactive adhesive system may be applied to the preformed bootor sheet, and Part B of the adhesive system may be applied to theprepared substrate. When the two sides are joined together, the adhesionchemistry is activated. In addition to the pure adhesive and primer, alayer of open mesh screen or fabric structure may be positioned inbetween the erosion protection layer and the substrate. The mesh orfabric serves as a physical gap to control the amount of the adhesivelayer, and also acts as a mechanical layer to assist the stripping ofthe erosion protection layer or as an erosion indicator to show that itis time to replace the protective material when the layer becomesvisible.

For non-aqueous or aqueous liquid materials, dry films of sufficientthickness were formed by spraying onto flat sheets or by casting theliquids in a “well” formed on flat substrate surrounded with gaskets orsealants. Another method is to use draw down gauge with sufficient gapto deposit sufficient amount of liquid onto the releasable sheets. Afterevaporation of the solvent or water and additional curing if needed, thedry films were removed. Polyethylene, polypropylene, silicone rubber,Teflon-coated aluminum, PP or PE-lined aluminum, or silicone fluidcoated glass plates can be used to construct the “welled” plates to fillthe liquid coating. For draw down or spraying, corona or flame treatedHDPE film (0.010″ thick) can be laminated to aluminum sheet to formreleasable substrates to form the film for tensile testing.

As noted above, at least one of the layers of the protective coatingformed from the coating composition advantageously has a tensilestrength of greater than or equal to about 1000 psi (70 kg/cm²), atensile elongation at break of greater than or equal to about 350% forsprayable coatings, a tensile set at break of less than or equal toabout 60%, a Shore A hardness of about 44 A to about 93 A and an 85degree gloss value of less than or equal to about 10.

The coatings obtained from the coating composition have a tensilestrength of greater than or equal to about 70 kg/cm². In one embodiment,the coatings have a tensile strength of greater than or equal to about105 kg/cm². In another embodiment, the coatings have a tensile strengthof greater than or equal to about 140 kg/cm². In yet another embodiment,the coatings have a tensile strength of greater than or equal to about210 kg/cm².

The coatings also advantageously have a tensile elongation at break ofgreater than or equal to about 350%. In one embodiment, the coatingshave a tensile elongation at break of greater than or equal to about425%. In another embodiment, the coatings have a tensile elongation atbreak of greater than or equal to about 550%. In yet another embodiment,the coatings have a tensile elongation at break of greater than or equalto about 600%. Sprayed coatings generally exhibit tensile elongations atbreak of greater than or equal to about 450%.

The coatings also advantageously have a tensile set at break of lessthan or equal to about 60%. In one embodiment, the coatings have atensile set at break of less than or equal to about 55%. In anotherembodiment, the coatings have a tensile set at break of less than orequal to about 50%. In yet another embodiment, the coatings have atensile set at break of less than or equal to about 40%.

The coatings obtained from the coating composition can be high gloss orlow luster. For military applications, an 85 degree gloss value of lessor equal to about 10 is generally desirable. In one embodiment, thecoatings have an 85 degree gloss of less than or equal to about 8. Inanother embodiment, the coatings have an 85 degree gloss of less than orequal to about 6. An exemplary value of 85 degree gloss is about 3 toabout 5.

The coating also advantageously displays a Shore A hardness of about 44A to about 93 A. In one embodiment, the coating displays a Shore Ahardness of about 55 A to about 90 A. In another embodiment, the coatingdisplays a Shore A hardness of about 65 A to about 85 A. In yet anotherembodiment, the coating displays a Shore A hardness of about 75 A toabout 83 A. An exemplary value of hardness for the coating is about 60to about 87 A.

The coating also advantageously displays a rain erosion resistance ofgreater than or equal to about 70 minutes, preferably greater than orequal to about 105 minutes and more preferably greater than or equal toabout 120 minutes, when subjected to a rain erosion test under condition1 described in the examples below.

As noted above, the coating can advantageously be used to protect theleading surfaces of airborne vehicles. The coating can be used toprotect aircraft wings, helicopter rotor blades, propeller blades, nosecones, radomes, fan blades, antennas, or the like, to protect them fromdamage due to rain, dust and/or sand. Other applications may includecoatings for gold balls, mining equipment, railcar liners, stone impactprotection coatings for motor vehicles, flexible adhesives, gap fillers,vibration and motion dampening, sound dampening, windshield crackfiller, noise control, electronic encapsulation, glass lamination,textile coatings, leather coatings, and other areas in which thesubstrates are subjected to damage caused by wear, abrasion, erosion,impact and vibration, or the like.

The following examples, which are meant to be exemplary, not limiting,illustrate compositions and methods for manufacturing the protectivecoatings described herein.

EXAMPLES

The physical properties were determined in test procedures similar tothat of ASTM D412-92 “Standard Test Methods for Vulcanized Rubber andThermoplastic Rubbers and Thermoplastic Elastomers-Tension”. However,modifications were made to reflect the unusual characteristics of thesematerials, as explained in discussions in the following paragraphs.

To prepare specimens for testing, different procedures were used toaccommodate the physical states of the materials. For tensile tests, itis desirable to use a dry film having a thickness of greater than orequal to about 0.006 inch (0.1524 millimeter). A preferred thickness ismore preferably about 0.008 inch (0.2032 millimeter). Lower thicknessescan give an artificially higher tensile strength due to dimensionalerrors.

The flexible, high elongation materials were tested using a ChatillonTCD 500 MH tensile tester, with 100 or 500 lb load cell and a Chatillondigital force gauge DFGS-R-ND. Both dumbbell shaped and straightrectangular specimens were used for the test. Straight specimens havinga 1 inch width (25.4 millimeters)×4.5 inches (114.3 millimeters) lengthwere used to prepare solvent based or water based coatings as well asthe test specimens.

Dumbbell shaped specimens having dimensions prescribed by ASTM D412 DieC are generally used when the straight rectangular specimens cannot bebroken or when they slipped out of the grips (sample holders used in atensile testing machine). Sheets with thickness of higher than 0.020″may preferably be tested with dumbbell shaped test specimens. Todetermine the sample thickness to be used in the calculation of tensileproperties, three thickness measurements are typically taken along bothsides of the specimens within the open gap space, noting the uniformityand value of sample thickness at the thinnest location on the samples.The thinnest measurement is used for calculation since it is the mostlikely location of the tensile break, unless it is noted that the breakpoint occurs at much different thickness locations. Data from defectivespecimens due to entrapped air bubbles or surface defects are not used.

Additional properties useful to determining high erosion resistance isthe tensile set at break (elastic recovery) and Shore A hardness. TheASTM procedures in D882, D2370 and D412 each by themselves were notsatisfactory for purposes of measuring each of these respectiveproperties in the erosion resistant materials.

Because of the very high elongation of these materials, a gripseparation speed of 20 inches per minute (508 millimeters per minute)was used. The distance between the grips (grip separation distance) wasset at 1 inch (25.4 millimeters) or 2 inches (50.8 millimeters) apart.This initial grip separation distance was used as the baseline forcalculation of the ultimate elongation at break. It was found that thesame material tested at 25.4 millimeter grip separation distance gave asubstantially higher percent elongation at break than a 50.8 millimetergrip separation distance. The grip separation distance of 50.8millimeters was therefore used for calculation of the ultimate percentelongation at break.

The ultimate percent elongation at break was defined as follows:Percent elongation=[(sample length at break−2 inches)/2 inches]×100

Because of the 8-ft ceiling of the test room and the set up of thegrips, the net available travel distance of the grips on the 30-inch TCD500 MH test machine was about 25 inches (625 millimeters). For thosethat did not break upon reaching the maximum height, the specimens werehand pulled till break to obtain the break force for use in calculatingthe tensile strength. The percent elongation at break for such samplesis recorded as 1250+%.

It was later found that slippage of the specimens from the gripscontributed to the artificially high values of elongation at break. Dueto the high tensile and high elongation at break properties of thesepolymers, it was determined that the 2 inch (50.8 millimeter) gapseparation distance was too large to break the specimens. It was decidedto change the starting grip distance to 1 inch (25.4 millimeter) and useASTM Die C for cutting test specimens, whenever the sample thickness washigher than 0.020 inch (0.508 millimeters), or if the specimens did notbreak when straight specimens were used for testing. To hold the testspecimens tighter, the Chatillon GF-9 Universal Tensile Grips were linedwith 200-grit sand paper over polyurethane sheet stock.

Other methods have been used in the industry to measure the tensileproperties. The procedure of ASTM D882-92 was tried, but was found notpractical. When used for 2 inch (25.4 millimeters) sample lengths andtensile elongation speeds of 20 inches/minute (508 millimeters/minute),the slippage of the test specimens inside the grip caused artificiallyhigh elongations at break. For ASTM D2370, the test calculates theelongation at break assuming no slippage inside the grips. However, forthe high tensile, high elongation materials of this invention, slippageinside the grips was a problem even with self-tightening grips linedwith high friction sand paper.

The ASTM D412-92 test procedure bench marks a 1 inch (25.4 millimeter)distance (Lo) in the middle of the dumbbell shaped or straight specimenand observes the elongated distance (L) between the bench marks at timeof break. The percent elongation at break (E) is calculated as100×(L−Lo)/Lo. In this method, the elongation away from the baseline canbe tracked on the digital display of the tensile test machine and whenthe specimen breaks and the machine stops, the actual travel distancecan be taken and used for purposes of calculation. Still, slippageinside the grip gave artificially high elongations at break.

Finally, a modified procedure was also tested. In this modifiedprocedure, the starting grip distance (distance between the grips) wasset at 1 inch (25.4 millimeters). Dumbbell shaped specimens arepreferred for use with samples having a thickness over 0.020 inches(0.508 millimeters) and straight specimens were preferred for sampleshaving thickness of about 0.006 (0.1524 millimeters) to about 0.020inches (0.508 millimeters). The choice of which geometry to use wasgenerally decided depending upon whether the material could be brokenwithin the thickness range using a particular configuration. Thepreferred specimen length was 3⅜ inches (85.725 millimeters) long. Benchmarks of 1 inch (25.4 centimeter) were marked on the center locations ofthe specimens. Each grip overlapped the positions of the bench marks. Asthe specimens were stretched, and as suspected, the initial bench markswere stretched out of the grip. The distance between the bench markswere tracked using the tensile test machine's digital display of“deflection” distance. At the same time, the distance between theelongated marks at the moment of tensile break was measured. For highelongation materials, the gap distance is to be monitored and measuredaccurately during tensile testing, as both sides of the bench marks aretraveling and expanding at the same time.

To determine the precise elongation, two persons are required, with oneperson holding a vertical ruler to track the location of the bottombench mark line, while the other tracks the reading of the upper benchmark line on the ruler. The observed elongated distance at break (L) wasused to calculate the percent elongation at break for the purpose ofthis invention as used in ASTM D412-92.

For comparison, the deflection on the tensile tester was set to zerodeflection at 1 inch (25.4 millimeters) grip separation, and the digitaldisplay of grip travel distance away from the initial 1 inch (25.4millimeters) distance was measured when the specimen broke. The distancewas divided by 1 inch (Lo) to calculate the percent elongation at break(slippage) for comparison. Since the digital deflection value is L−Lo,this is mathematically the same as 100(L−Lo)/Lo. The results indicatethat even with self-tightening grips, the slippage inside the gripscaused artificially high elongation at break of up to 2486% (machinelimit), while the elongation at break as defined by the test method ofthis invention is substantially lower. These results indicate that ASTMD882 is not a good test procedure for high strength, high elongationelastic materials.

The elastic recovery after tensile stretch is a useful property forascertaining the erosion resistance of coatings. There is no referenceto this property in the ASTM D882 test method. For purposes ofcalculating the tensile set at break, ASTM D412-92 defines the tensileset (E) as E=100 (L−Lo)/Lo, wherein L is the distance between the benchmarks after a 10 minute retraction period, while Lo is the initialdistance between the benchmarks. The criteria prescribed by ASTM D412-92are not sufficient to determine good erosion resistant materials becausein reality the raindrops can impact the erosion resistant coating atintervals of less than or equal to about 2 minutes. A good measure todetermine whether a material is suitable for erosion protection istherefore to measure the tensile set immediately after tensile break assoon as possible. As noted above, two lines with a separation distanceof 1 inch (2.54 millimeter) are marked on the test specimens and usedfor the elongation at break test. After the test specimens break on thetest stand, they were taken down and were reassembled. The distancebetween the line marks were measured and used to calculate the TensileSet at Break (Recovery). The time to take the measurements is about 30to 60 seconds after the specimen breaks. For the purpose of thisinvention, the Tensile Set Recovery is defined as the (L−Lo)/Lo, inwhich the L is distance of the lines measured after tensile break within30 seconds to one minute and Lo is the original distance of 1 inch (25.4millimeters).

To determine the Shore A hardness of the materials, ASTM D2240 procedurewas used. A PTC 306L Type A Durometer with 471 1 kilogram DeadweightTest Stand was used. The test readings include the readings upon firstcontact and the readings after 15 seconds (i.e., Example 1, expressed as“82 to 64 A” indicating an initial value of 82 A and value taken 15seconds later of 64 A). For a highly elastomeric material (“liverubber”), the initial Shore A reading is the same as it is after aperiod of time with the durometer held in firm contact with the specimensurface. If the specimen is quite plastic, a more rapid receding to asubstantially lower hardness reading is observed with the passage oftime. The receding of the hardness is also called “Creep”.

For thin coating samples, multiple layers of the coatings were stackedup to a thickness of greater than or equal to about 0.120 inches (3.04millimeters) for measurement. The hardness of the polyurethaneelastomers varies with temperature, and the hardness generally increaseswith a decrease in temperature. The hardness tests were performed at atemperature of about 68 to about 82° F. While Shore A hardness of thesofter materials seemed to vary with the 14° F. difference, the range ofeffective Shore A hardness as defined later is functional.

As detailed below, the following tests were conducted on the erosionresistant coatings. Desirable properties and characteristics are listedbelow.

Tensile strength: In order to resist the cutting and tearing from theimpact of the raindrops or sand particles at high speed, the materialmust have sufficient tensile strength. The tensile strength requirementsfor the erosion resistant coatings is about 70 kg/cm² to about 210kg/cm² for polyurethanes. It is generally desirable for the erosionresistant coating to have a minimum tensile strength of 70 kg/cm²,preferably greater than or equal to about 140 kg/cm².

Percent elongation at break: Considering that the typical aircraftsubstrates are very rigid and have percent elongation at break of lessthan 100% and that the erosion resistant coatings are applied at athickness of about 0.014 inches (0.3556 millimeter), it is quitedifficult to imagine that a highly erosion resistant material needs tohave very high percent elongation at break. Commercially availablematerials generally show that the minimum of percent elongation at breakis about 300 to about 350% and their product datasheets disclose thatthe typical values of percent elongation at break are about 500% forglossy coatings and about 300% for lusterless sprayable coatings. Theprior art materials of the lusterless coatings did not exceed 300% inelongation. It has been discovered that that the elongation at breakvalues of a highly erosion resistant sprayable low luster coating isgreater than or equal to about 400%, preferably greater than or equal toabout 425%, more preferably greater than or equal to about 500%, andmost preferably greater than or equal to about 550%.

Tensile set recovery: A material having very high percent elongation(e.g., greater than or equal to about 400%) is not always a good erosionresistant material. When a material is highly stretchable with very highelongation, it may stay stretched with poor recovery after tensilebreak. It has discovered that in order to resist the rain erosion, thematerial should display a tensile set at break of less than 150%, morepreferably less than 73% and most preferably less than 60% in additionto a high elongation at break of greater than or equal to about 350%.The value of this property is generally due to the nature of rainerosion. Raindrops impact the substrate in an intermittent pattern. Ingeneral, no particular location on a surface is continuously impacted byrain drops. Instead, the raindrops impact the surface in an irregular,intermittent manner, at varying short intervals. After having resistedthe cutting and tearing of the rain drops because of its high elongationto break, the material should be able to recover very quickly in orderto face another wave of impact damage from the raindrops. It istherefore desirable for the material to have a high tensile strength, ahigh elongation, as well as recover sufficiently from tensile stretch inorder to provide suitable protection against rain erosion.

Shore A Hardness: The importance of Shore A hardness in a good erosionresistant material is its ability to absorb impact energy and to bendunder impact. It has been discovered that polyurethane materials stiffensubstantially with decrease in temperature. It is desirable for theShore A values at 68° F. to be less than or equal to about 95 A. Themost preferred Shore A range is about 44 to about 93 A.

Rain Erosion Test Condition 1: The specimens were also tested at the AirForce Research Lab Rain Erosion Test Facility, Wright-Patterson AirForce Base, Dayton, Ohio. Predominant rain drop size rate is about 1.8to about 2.2 millimeters diameter. The rainfall rate is set at one inchper hour. The erosion resistance of a coating can be judged by combiningthe information of total rain erosion test time and the degree oferosion on the specimens. The failure of the coating is usually the timewhen the erosion reaches the substrate.

In the following examples, aluminum airfoil substrates were used. Awater reducible epoxy primer Deft 44GN063 was used except where it isnoted. The aluminum airfoil was blasted with 100 grit aluminum oxide,detergent cleaned and water rinsed, dried, and Alodine 1200S treated.The airfoil was then primed coated with one coat of 44GN063. The primedairfoils may be heated at 50° C. for 20 minutes to speed up the dryingand curing, or left at room temperature, typically for 1 to 2 hoursbefore applying the top coat layer with the polyurethane coatingcompositions.

The base coat layer is used to build up the thickness, with the top coatlayer having the matte surface finish applied in one or two coats.

The following ingredients used in the formulations are shown in Table 1:

TABLE 1 Ingredient Details Prepolymers Varies according to example.Disperbyk 166 dispersant from BYK-Chemie. Stan-Tone White HCC-19590 60%TiO2 in plasticizer, from Poly- One. Stan-Tone Black HCC-7198 20% carbonblack in plasticier, from Poly-One. Gray color concentrate (HCC-19590white/HCC-7198 black at HT92-158A 75/5 weight ratio) Gray colorconcentrate (water based gray color concentrate P94-131-1A 92.39%UCD-1106E white/7.61% UCD-1507E black) Defoamer concentrate: Byk 051used as 2% in solvent (toluene or butyl acetate) Wetting agentconcentrate: Silwet L7602, used as 2% in solvent Silwet L7602 (tolueneor butyl acetate) UV stabilizer UV92-243-1 39.49% solid content of 2/2/1by weight mixture of Tinuvin 123/Tinuvin 328/ Irgonox 1135 in solvent(toluene or butyl acetate) Hydrolysis stabilizer Staboxol P200, 50% intoluene Flatting agent concentrate #1 5.97% Acematt TS-100 dispersedwith 2.95% Disperbyk 103 in solvent. Solvent may be n-propyl acetate, n-butyl acetate, PM acetate, MAK, MIBK, toluene or mixtures of the above.Moisture reduced to below 0.04% by treating with molecular sieves.

Example 1

This example demonstrates the use of TDI-ester with polyaspartic esterof this invention. An aluminum airfoil primed with a water based epoxyprimer was coated with eight coats of a glossy gray coating compositionto form a base coat (#1B) layer comprising a TDI-ester prepolymer and apolyaspartic ester curative. After drying for about one hour at roomtemperature, one coat of a matte coating was sprayed over the glossybase coat. The matte top coat layer (#1T) was a polyurethane coatingcomprising a toluene diisocyanate-polytetramethylene glycol (TDI-PTMEG)prepolymer and an aldimine curative. The dry protective coatingthickness at the leading edge measured about 0.018 inches. The coatingwas cured at ambient temperature and humidity. The dried airfoil had a85 degree gloss of 5.8.

The coated airfoil was subjected to Rain Erosion Test Condition 1. After155 minutes, the specimen show minor pitting and cratering, with onlyone site eroded all the way to the substrate.

The Gloss Basecoat #1B was prepared as follows: A gray pigmentedconcentrate of a TDI-ester prepolymer, Versathane D-5QM, with anisocyanate content of 4.99%, available from Air Products Chemicals wasprepared by mixing the following ingredients in a mechanical mixer witha high shear mixing blade until uniformly dispersed. The ingredients areshown in Table 2.

TABLE 2 Basic ratio Actual weight 25  1309 g of Versathane D-5QM  6.25327.4 g of Solvent blend (toluene/MIBK/xylene, at 1/1/2 ratio by weight) 1.00 52.36 g of Disperbyk 166, available from BKY-Chemie. Used as 5%concentrate in toluene.  1.55 81.78 g of gray pigment conctrate(HCC-19590 white/HCC-7198 black at 75/5 weight ratio)  0.60 31.41 g ofwetting agent concentrate  0.30 15.77 g of defoamer concentrate *g =grams

The final coating composition was prepared by mixing the followingingredients together: 70.0 g of the above gray prepolymer concentrate,2.64 g of UV92-243-1, 2.12 g of hydrolysis stabilizer, 47.68 g offlatting agent concentrate (in a mixture oftoluene/xylene/PMAcetate//n-propyl acetate/n-butyl acetate/MAK, rationot critical), 19.91 g of polyaspartic ester Desmophen NH1420 (used as80% mixture in xylene),

8.10 g of 2% organic acid (Industrene 206) in toluene, 31.0 g of MAK(methyl n-amyl ketone). The above ingredients were mixed with a highshear mixer blade in a plastic container until fully dispersed. Thesolution has a Brookfield viscosity of 96 cps.

The solution sprayed and flowed very well using a small conventionalspray gun. A spray dried film of the composition has a 60 degree/85degree gloss of 38/55. When the solution was draw-down on a releasableplastic plate, and subject to drying at 20° C. for 16 hours and then 30°C. for 2 days. When a 0.006 inch (0.152 millimeter) thick specimen wastested later under the modified tensile test procedure detailed above,using 1 inch as the distance of jaw separation, the coating had atensile strength of 7233 psi, 525% elongation at break, 26% tensile setrecovery and a shore A hardness of 82-62 A at 68° F. (82 A was thehardness upon first contact and 62 A was the hardness after 15 minutes).If slippage in the tensile specimen holder is allowed into thecalculation, the elongation at break was 1237%.

The Matte Topcoat #1T was prepared as follows: An 80% by weightprepolymer solution was prepared by mixing an equal part of TDI-PTMEGprepolymer (Airthane PET-85A, NCO=3.33%) to another equal part of aTDI-PTMEG prepolymer (Airthane PET-93A, NCO=5.24%) in a solvent mixtureof 1/1/1 by weight n-Propyl acetate/n-Butyl acetate/PMAcetate.

A gray pigmented prepolymer solution was prepared by mixing thefollowing ingredients with a high shear mixing blade till uniformlydispersed.

1479.69 g of the above 80% prepolymer solution, 47.35 g of 5% Disperbyk166 in toluene and 73.39 g of gray pigment concentrate HT92-158A

The final matte topcoat solution was mixed with a high shear mixingblade according to the following ratio:

-   -   51.60 g of the above gray prepolymer solution,    -   1.38 g of UV stabilizer UV92-243-2,

76.38 g of flatting agent concentrate (in a mixture oftoluene/xylene/PMAcetate//n-propyl acetate/n-butyl acetate/MAK).Moisture controlled to below 0.04% with molecular sieve, ground by ahigh shear homogenizer Diax 600.

-   -   5.10 g of Aldimine Desmophen PAC XP7076    -   3.00 g of 2% organic acid (Industrene 206) in toluene    -   0.47 g of defoamer concentrate    -   32.00 g of 1/1/2 n-Propyl acetate/n-butyl acetate/PMAcetate

The solution had a viscosity of 80 cps. When sprayed onto a substrate,the dried coating had a 60 degree/85 degree surface gloss of 2.3/3.9. A0.009 inch thick sheet of the cured coating had a tensile strength of6000 psi, an elongation at break of 575%, a tensile set recovery of 22%.The elastomer had a Shore A hardness of 82-71 A at 68° F. If slippage inthe tensile specimen holder is allowed in the calculation, theelongation at break was 1679%.

Example 2

This example demonstrates the use of TDI-ether with polyasparticesters-aldimine curing agent mixture of this invention:

In a procedure similar to Example 1 above, three coats of glossyurethane basecoat (#2B1), five coats of gloss urethane basecoat (#2B2)and one coat of matte urethane topcoat (#2T) were sprayed on an epoxyprimed aluminum airfoil. The dry coating thickness at the leading edgemeasured about 0.020 inches. The matte topcoat by itself had an 85degree gloss of 3.5. The dried airfoil had an 85 degree gloss of 3.5.The coated airfoil was subjected to Rain Erosion Test Condition 1. After160 minutes, two craters were formed, one of which extended to thesubstrate. A few tiny pits were noticed. The topcoat adhesion wasadjudged to be excellent.

The gloss gray basecoats were based on a TDI-PTMEG prepolymer andaldimine/aspartic ester curative mixture at 1/2 molar ratio. The mattetopcoat was based on TDI-PTMEG prepolymer and aldimine curative.

The Gloss Basecoat #2B1 with 2% by weight of flatting agent was preparedas follows: A gray pigmented concentrate of a TDI-PTMEG prepolymer,AIRTHANE PET-93A, with an isocyanate content of 5.23%, available fromAir Products and Chemicals was prepared by mixing the followingingredients in a mechanical mixer with a high shear mixing blade. Theingredients are shown in Table 3 below:

TABLE 3 Basic Ratio Actual Weight 31.25 1600 g of 80% Airthane PET-93Ain 1/1/1 n-Propyl acetate/n-butyl acetate/PMAcetate  1.00 51.26 g of 5%Disperbyk 166 in toluene  1.55 79.70 g of Gray color concentrateHT92-158A  0.60 30.72 g of wetting agent concentrate

The final solution was prepared by mixing the following ingredients withhigh shear mixing blade till uniformly dispersed.

-   -   86.0 g of the above gray prepolymer concentrate    -   2.50 g of UV92-243-2    -   28.70 g of flatting agent concentrate (in a mixture of        toluene/xylene/PMAcetate//n-propyl acetate/n-butyl acetate/MAK.        Diax 600 homogenizer ground for 3 minutes),    -   21.80 g of a curing agent concentrate, made of 15.93% by weight        of Aldimine Desmophen PAC XP7076, 64.07% by weight of        Polyaspartic ester Desmophen NH1402 and 20% of xylene. The molar        ratio of XP7076/NH1402 is 1/2.    -   5.0 g of 2% organic acid (Industrene 206) in toluene, 10 g of        MAK 42 g of PMAcetate.    -   0.75 g of defoamer concentrate.

The above ingredients were mixed with a high shear mixer blade in aplastic container until fully dispersed. The solution has a viscosity of108 cps.

Another Gloss Basecoat #2B2 was prepared with flatting agent at 4% ofthe resin solid as follows:

-   -   86.0 g of the above gray prepolymer concentrate    -   2.50 g of UV92-243-2    -   57.4 g of flatting agent concentrate (in a mixture of        toluene/xylene/PMAcetate//n-propyl acetate/n-butyl acetate/MAK.        Diax 600 homogenizer ground for 3 minutes),    -   21.72 g of a curing agent concentrate, (15.93% by weight of        Aldimine Desmophen PAC XP7076, 64.07% by weight of Polyaspartic        ester Desmophen NH1402 and 20% of xylene). The molar ratio of        XP7076/NH1402 is 1/2.    -   26 g of 1/1/2 n-Propyl acetate/n-butyl acetate/PMAcetate.    -   0.75 g of defoamer concentrate.

The solution had a viscosity of 118 cps. After curing, a 0.008″ thickgloss basecoat #2B2 had a tensile strength of 3775 psi, an elongation atbreak of 525%, and a tensile set recovery of 10.2%. The elastomer had aShore A hardness of 67 to 53 A at 68° F. When measured with slippage injaw at 1″, the elongation at break was 1320%.

The Matte Topcoat #2T

The composition of matte topcoat #2T is similar to that of matte topcoat#1 except that slightly lower amount of flatting agent was used and themixing was done with high shear dispersion blade without the use of ahomogenizer Diax 600. The formulation was as follows:

-   -   51.6 g of the gray prepolymer solution    -   1.35 g of UV stabilizer UV92-243-2    -   72.5 g of flatting agent concentrate (in a mixture of        toluene/xylene/PMAcetate//n-propyl acetate/n-butyl acetate/MAK.        Moisture controlled to below 0.04% with molecular sieve)    -   5.10 g of Aldimine Desmophen PAC XP7076    -   3.00 g of 2% organic acid (Industrene 206) in toluene    -   20.00 g of 1/1/2 n-Propyl acetate/n-butyl acetate/PMAcetate

The coating has a viscosity of 112 cps. The cured matte coating at0.014″ thick, had a tensile strength of 5914 psi, an elongation at breakof 525% and a tensile set recovery of 18%. When measured with slippagein jaw at 1″, the elongation at break was 1613%. The matte elastomer hada Shore A hardness of 82-73 A at 68° F.

Example 3

This example demonstrates the use of TDI-ester-aspartic ester basecoatwith H12MDI PTMEG-aldimine-aspartic ester matte topcoat. In a proceduresimilar to Example 1 above, eight coats of Gloss Basecoat #3B and onecoat of Matte Topcoat #3T were sprayed on an epoxy primed aluminumairfoil. The dry coating thickness at the leading edge measured about0.019 inches. The dried airfoil had a 60 degree/85 degree gloss of1.8/3.8. The coated airfoil was subjected to Rain Erosion Test Condition1 for 140 minutes with moderate damage. Excellent topcoat adhesion wasobserved.

The gloss gray basecoat #3B was based on a TDI-ester prepolymer andaldimine curative. The matte topcoat was based on H12MDI-PTMEGprepolymer and aldimine-polyaspartic ester mixture curatives. The GlossBasecoat #3B was prepared as follows:

A gray pigmented concentrated of an TDI-terminated polyester prepolymer,VERSATHANE A-9QM, with isocyanate content of 4.28%, available from AirProducts and Chemicals was prepared by mixing the following ingredientsin a mechanical mixer with a high shear mixing blade. The ingredientsare shown in Table 4.

TABLE 4 Basic Ratio Actual Weight 31.25 1600 g of Versathane A-9QM, 80%in toluene/MIBK/xylene (1/1/2 ratio by weight)  1.00 51.20 g of 5%Disperbyk 166 in toluene  1.55 79.36 g of gray pigment conctrateHT92-158A  0.60 30.72 g of wetting agent concentrate  0.30 15.36 g ofdefoamer concentrate

The final coating solution was prepared as in the following ratio:

-   -   86.75 g of the above gray prepolymer concentrate,    -   2.85 g of UV92-243-1,    -   2.30 g of hydrolysis stabilizer,    -   50.98 g of flatting agent concentrate (5.97% TS-100 in a mixture        of toluene/xylene/PMAcetate//n-propyl acetate/n-butyl        acetate/MAK),    -   8.50 g of aldimine Desmophen PAC XP7076,    -   4.4 g of 2% organic acid in toluene, (Industrene 206),    -   20.0 g of MAK.

The above ingredients were mixed with a high shear mixer blade in aplastic container until fully dispersed. The solution has a viscosity of100 cps. The cured gloss basecoat #3B, at 0.012″ thickness, showed atensile strength of 6500 psi, an elongation at break of 675% and atensile set recovery of 30%. When the slippage in the jaw was ignored,the elongation at break was 1845%. The gloss basecoat had a Shore Ahardness of 78-70 A at 68° F.

The Matte Topcoat #3T was prepared as follows:

A gray pigmented concentrate of an H12MDI-PTMEG prepolymer, ADIPRENELW520, with isocyanate content of 4.81%, available from UniroyalChemical was prepared by mixing the following ingredients in amechanical mixer with a high shear mixing blade. The ratios are shown inTable 5 below.

TABLE 5 Basic Ratio Actual Weight 31.25 2532.0 g of Adiprene LW520, NCO= 4.81%, 80% in n- propyl acetate/n-butyl acetate/PMAcetate (1/1/1 byweight)  1.00 81.08 g of 5% Disperbyk 166, in toluene  1.55 125.60 g ofgray pigment concentrate HT92-158A  0.60 48.61 g of wetting agentconcentrate  0.30 48.70 g of defoamer concentrate

The final matte coating solution was prepared as in the following ratio:

-   -   52.50 g of the above gray prepolymer concentrate,    -   1.47 g of UV92-243-2,    -   1.14 g of aldimine Desmophen PAC XP7076,    -   7.63 g of polyaspartic ester Desmophene NH1220    -   82.50 g of flatting agent concentrate (5.97% TS-100 in a mixture        of n-propyl acetate/n-butyl acetate/PMAcetate (1/1/2),    -   3.00 g of 2% organic acid in toluene, (Industrene 206),    -   15.0 g of PMAcetate

The matte coating solution has a viscosity of 115 cps. When sprayed onecoat over a substrate, the 60/85 degree gloss was 2.0/3.3. After curing,a 0.008″ thick sheet of the matte coating showed a tensile strength of5575 psi, an elongation at break of 525%, and a tensile set recovery of18%. When the slippage in the jaws (grips) was ignored, the elongationat break was 1470%. The cured matte topcoat had a Shore A hardness of81-72 A at 68° F.

Example 4

This example demonstrates the use of regular aromatic diamine with thealdimine with TDI-ester prepolymer.

The Gloss Basecoat #4B was prepared as follows: A black pigmentedconcentrate of an TDI-ester prepolymer, VERSATHANE A-85QM, withisocyanate content of 3.61%, available from Air Products and Chemicalswas prepared by mixing the following ingredients in a mechanical mixerwith a high shear mixing blade. The ratios are shown in Table 6.

TABLE 6 Basic Ratio Actual Weight 31.25 1254 g of Versathane A-85QM, 80%in toluene/MIBK/xylene (1/1/2 ratio by weight)  1.58 63.40 g of HCC-7198black pigment concentrate  0.60 24.08 g of wetting agent concentrate 0.30 24.16 g of defoamer concentrate

The final coating solution was prepared as in the following ratio:

-   -   68.06 g of the above black prepolymer concentrate,    -   1.76 g of hydrolysis stabilizer,    -   4.0 g of 2% organic acid in toluene, (Industrene 206),    -   34.0 g of PMAcetate    -   10.42 g of aldimine/amine concentrate made of 41.26% of aldimine        Desmophen PAC XP7076, 8.74% Ethacure 100, 50.0% Toluene. All        ratio by weight. Mixture is aldimine/aromatic amine at 3/1 molar        ratio,

The above ingredients were mixed with a high shear mixer blade in aplastic container until fully dispersed. The solution has a viscosity of113 cps. The cured gloss basecoat #4B, at 0.012″ thickness, showed atensile strength of 3567 psi, an elongation at break of 725% and atensile set recovery of 18%. When the slippage in the jaw was ignored,the elongation at break was 1969%. The gloss basecoat had a Shore Ahardness of 52 to 45 A at 68° F.

The Matte Topcoat #3T was prepared as follows:

The final coating solution was prepared as in the following ratio:

-   -   34.03 g of the above black prepolymer concentrate,    -   0.88 g of hydrolysis stabilizer,    -   2.0 g of 2% organic acid in toluene, (Industrene 206),    -   42.40 g of flatting agent concentrate (5.97% TS-100, 2.95%        Disperbyk 103 in a mixture of 1/2 toluene//MAK. Moisture reduced        to 0.02% with molecular sieve),    -   5.21 g of aldimine/amine concentrate made of 41.26% of aldimine        Desmophen PAC XP7076, 8.74% Ethacure 100, 50.0% Toluene. All        ratios are by weight. Mixture is aldimine/aromatic amine at 3/1        molar ratio,

The matte coating solution has a viscosity of 52 cps. When sprayed onecoat over a substrate, the 60/85 gloss was 1.0/3.1. After curing, a0.017″ thick sheet of the matte coating showed a tensile strength of5282 psi, an elongation at break of 800%, and a tensile set recovery of46%. When the slippage in the jaw was ignored, the elongation at breakwas 2337%. The cured matte topcoat had a Shore A hardness of 81 to 67 Aat 68° F.

Eight coats of the gloss basecoat and one coat of the matte topcoat weresprayed onto an epoxy primed aluminum airfoil. The dry film thickness atthe leading edge was 0.011 inch. The dried airfoil had a 60/85 degreegloss of 0.9/3.5. It was subjected to rain erosion test condition 1.After 115 minutes, there was moderate damage with damage at three sitesextending to the substrate.

Example 5

This example demonstrates the use of water based coating with solventbased coating of this invention, and the protective effect of highelongation matte topcoat on low elongation gloss basecoat.

Eight coats of water-based gloss urethane basecoat #5B, one coat ofsolvent based matte urethane topcoat #5T1 and another coat of solventbased matte urethane topcoat #5T2 were sprayed on an epoxy primedaluminum airfoil. The dry coating thickness at the leading edge measuredabout 0.021 inches. The dried airfoil had a 60/85 degree gloss of1.2/2.2. The coated airfoil was subjected to Rain Erosion TestCondition 1. After 113 minutes, only three craters and a few pits @113min. Not failed yet.

The gloss gray basecoat was a blend of water dispersion of polyurethanepolymers with additional epoxy crosslinking agent. The matte topcoatswere a solvent based urethane coating based on TDI-PTMEG prepolymer andaldimine. This example describe that, when more than one coatings areused, at least one of the coatings is preferably over 425% elongation.

Gloss Basecoat #5B

5 parts of a water based aliphatic-ether polyurethane dispersionHD-2024, available from Hauthaway, was mixed with 1 part of aliphaticpolyurethane dispersion UNITHANE RI. The resulting coating had 43.3%solid.

The gloss basecoat was prepared by mixing the following together:

-   -   302.35 g of the above water based polyurethane dispersion    -   10.50 g of Gray color concentrate P94-131-1A    -   7.02 g of HA806 (water dispersible epoxy curing resin from        Hauthaway)    -   4.22 g of UV92-243-10 (2/2/1/5 by weight mixture of Tinuvin        213/Tinuvin 292/Irganox 1135/n-methyl pyrrolidone)    -   11.0 g of distilled water    -   10 drops of defoamer (Dapro DF2162)

The coating had a Brookfield viscosity of 50 cps. After drying andcuring, the coating had an average tensile strength of 2077 psi, anelongation at break of 380%, and a tensile set recovery of 15%. Thegloss basecoat had a Shore A hardness of 80 to 60 A at 68° F.). TheMatte Topcoat #5T1 was prepared as follows:

A gray pigmented prepolymer solution was prepared by mixing thefollowing ingredients with a high shear mixing blade till uniformlydispersed.

-   -   463.14 g of an 80% prepolymer solution (Airthane PET-85A,        NCO=3.33%) in 1/1/1 n-propyl acetate/n-butyl acetate/PMAcetate,    -   470.0 g of an 80% prepolymer solution (Airthane PET-93A,        NCO=5.23%) in 1/1/1 n-propyl acetate/n-butyl acetate/PMAcetate,    -   29.93 g of 5% Disperbyk 166 in toluene    -   46.50 g of gray pigment concentrate HT92-158A    -   29.84 g of wetting agent concentrate    -   17.90 g of defoamer concentrate

The final matte topcoat solution #5T1 was mixed with a high shear mixingblade according to the following ratio:

-   -   35.40 g of the above gray prepolymer solution    -   3.42 g of Aldimine Desmophen PAC XP7076    -   2.00 g of 2% organic acid (Industrene 206) in toluene    -   47.66 g of flatting agent concentrate (in a 1/1/2 by weight        mixture of/n-propyl acetate/n-butyl acetate/PMAcetate. No        moisture scavenger used.))    -   24.00 g of 1/1/2 n-Propyl acetate/n-butyl acetate/PMAcetate

The solution has a viscosity of 133 cps. When sprayed onto a substrate,the dried coating had a 60/85 degree surface gloss of 1.9/3.0.

A 0.013″ thick sheet of the cured coating had a tensile strength of 4852psi, an elongation at break of 600%, a tensile set recovery of 22%. Theelastomer had a hardness of 74-56 A at 68° F. If slippage in the tensilespecimen holder is ignored, the elongation at break was 1720%.

Another matte topcoat #5T2 was prepared the same way as #5T1, exceptthat 20.0 grams of 1/1/2 n-Propyl acetate/n-butyl acetate/PMAcetate wasused. The flatting agent concentrate was treated with moisture scavengerto reduce the moisture content to 0.029%. The sprayed dried #5T2 coatinghad a 60/85 degree surface gloss of 1.1/2.1.

A 0.015″ thick sheet of the cured coating had a tensile strength of 4600psi, an elongation at break of 600%, a tensile set recovery of of 22%.The elastomer had a hardness of 83-68 A at 68° F. If slippage in thetensile specimen holder is ignored, the elongation at break was 1754%.

Example 6

This example demonstrates the use of water based basecoat and mattetopcoat and the significance of combined tensile properties disclosed inthis invention to the erosion resistance of the elastomer.

23 coats of water based urethane gloss basecoat and one coat of waterbased matte urethane topcoat were sprayed on an epoxy primed aluminumairfoil. The dry coating thickness at the leading edge measured about0.027 inches. The dried airfoil had an 85 degree gloss of 3.0. Thecoated airfoil was subjected to Rain Erosion Test Condition 1. After 135minutes, only crater and one tiny surface pit after 135 min. Not tosubstrate yet.

The gloss gray basecoat was a water dispersion of polyurethane polymerwithout additional crosslinking agent. The matte topcoat was the samecomposition with additional matting agent added.

Gloss Basecoat #6B:

The gloss basecoat #6B was prepared by mixing the following ingredientswith high shear mixing blade till uniformly dispersed.

-   -   665.94 g of HD-2024 water based aliphatic polyether polyurethane        dispersion, available from Hauthaway,    -   24.02 g of gray concentrate HT86-237G    -   79.50 g of distilled water    -   3.0 g of 5% Silwet L7602 wetting agent    -   30 drops of defoamer DF2162

The coating had a Brookfield viscosity of 130 cps. A 0.030″ thick drygloss basecoat showed a tensile strength of 2010 psi, an elongation atbreak of 675%, a tensile set recovery of 46%. If slippage in the tensilespecimen holder is ignored, the elongation at break was 1425%. Theelastomer had a hardness of 58-42 A at 68° F.

The matte topcoat #6T was prepared by mixing the following ingredientswith high shear mixing blade till uniformly dispersed.

-   -   332.99 g of HD-2024 water based aliphatic polyether polyurethane        dispersion, available from Hauthaway,    -   12.05 g of gray concentrate HT86-237G    -   163.22 g of distilled water    -   29.89 g of Lo-Vel 2000 silica flatting agent    -   1.52 g of 5% Silwet L7602 wetting agent    -   15 drops of defoamer DF2162

The coating had a Brookfield viscosity of 167 cps. A 0.036″ thick drymatte basecoat showed a tensile strength of 2778 psi, an elongation atbreak of 650%, a tensile set recovery of 73%. If slippage in the tensilespecimen holder is ignored, the elongation at break was 1383%. Theelastomer had a hardness of 86-81 A at 70° F.

Comparative Example 1: Caapcoat FP-250

Caapcoat FP-200, a glossy sprayable polyurethane coating based onisocyanate terminated polyester prepolymer and an aliphatic amine, Thecoating as mixed had a viscosity of 215 centipoises and was thinned witha 1/1/2 mixture of toluene/MIBK/xylene to a viscosity of 149 cps.Twenty-five coats of FP-200 was sprayed on an aluminum airfoil primedwith Aeroglaze 9947. After waiting for two hours to allow the basecoatto dry to prevent mud cracking of the topcoat, the lusterless topcoatFP-050 was sprayed over the gloss basecoat. The dried coating thicknesswas about 0.020″. The airfoil had a 85o gloss of 2.5. The cured airfoilwas subjected to Rain Erosion Test Condition 1. The specimen showedwidespread erosion to the substrate at 36 minutes and was stopped at 41minutes.

The gloss basecoat FP-200 showed an average tensile strength of 4604psi, an average elongation at break of 425%, a tensile set recovery of10%. The elastomer has a Share A hardness of 77-68B at 70 F.

The matte topcoat FP-050 showed a an average tensile strength of 5148psi, an elongation at break of 362%, a tensile set of 22%, and Shore Ahardness of 84-78 A.

While the invention has been described with reference to exemplaryembodiments, it will be understood by those skilled in the art thatvarious changes may be made and equivalents may be substituted forelements thereof without departing from the scope of the invention. Inaddition, many modifications may be made to adapt a particular situationor material to the teachings of the invention without departing from theessential scope thereof. Therefore, it is intended that the inventionnot be limited to the particular embodiment disclosed as the best modecontemplated for carrying out this invention, but that the inventionwill include all embodiments falling within the scope of the appendedclaims.

What is claimed is:
 1. An erosion resistant article comprising anairfoil shaped substrate having a leading edge surface exposed in use tohigh speed impingement of liquid or solid particles, said leading edgesurface covered with a protective coating comprising: a polyurethane orpolyurea coating selected from the group consisting of anisocyanate-terminated prepolymer cured with a curing agent, apolyisocyanate cured with a curing agent, and a water dispersion of apre-reacted polyurethane, said curing agent selected from a groupconsisting of an aldimine, a ketimine, a polyaspartic ester, apolyamine, one or more polyols and mixtures thereof having a tensilestrength greater than 1000 psi (70 kg/cm²), an elongation at breakgreater than 350%, a tensile set of less than 150%, and a Shore Ahardness of 44 A to 95 A as measured at 68° F. when tested without anyfiller.
 2. The erosion resistant article of claim 1 wherein saidpolyurethane or polyurea coating is preformed into a cured form selectedfrom the group consisting of boots, films, sheets, and tapes.
 3. Theerosion resistant article of claim 2 further comprising an underlyinglayer of primer or an adhesive material bonding said preformed sheet tosaid airfoil shaped substrate.
 4. The erosion resistant article of claim2 wherein said polyurethane or polyurea coating is preformed into acured sheet or tape.
 5. The erosion resistant article of claim 2 whereinsaid cured form is a boot preformed to have the shape of the leadingedge of the airfoil shaped substrate.
 6. The erosion resistant articleof claim 2 wherein said cured form is adhesively bonded onto the airfoilshaped substrate.
 7. The erosion resistant article of claim 1 whereinsaid polyurethane or polyurea coating having incorporated therein atleast one filler selected from a group consisting of metal powders,metal flakes, metal fibers, milled metal fibers, metal-coated syntheticfibers, metal-coated glass spheres, metal-coated hollow spheres,graphite, carbon nanotubes, vapor grown carbon fibers, carbon fibers,milled carbon fibers, carbon coated synthetic fibers, buckyballs,electroactive polymers, conductive metal oxides, tertiary ammonium saltcompounds, carbon blacks, coke, alumina, boron nitride, aluminumnitride, silica coated aluminum nitride, silicon carbide, silicas, fumedsilicas, silicates, talc, calcium carbonate, polymer beads, ureaformaldehyde, metal oxides, radar absorbing materials, microballoons,polytetrafluoroethylenes, polyolefins, polyamides, polyimides,polysilazanes, polysiloxanes, fluoropolymers, and mixtures thereof. 8.The erosion resistant article of claim 1 wherein said polyurethane orpolyurea coating has incorporated therein at least one organic basedpowder selected from the group consisting of polycarbonate,polyetherimide, polyester, polyethylene, polysulfone, polystyrene,acrylonitrile-butadiene-styrene block copolymer, Teflon, fluoropolymers,polypropylene, acetal polymers, polyvinyl chloride, polyurethanes, nylonand mixtures of any of the foregoing fillers.
 9. The erosion resistantarticle of claim 1 wherein the airfoil shaped substrate with a leadingedge is a portion of an article selected from the group consisting of anaircraft wing, a rotor blade, a turbine blade, a propeller blade, aradome, an antenna, a fan blade and a nose cone.
 10. The erosionresistant article of claim 2 wherein said preform is formed over areleasable structure of similar dimension and configuration of saidleading edge surface of said airfoil shaped substrate.
 11. The erosionresistant article of claim 1, wherein the isocyanate-terminatedprepolymer is made from diisocyanates selected from the group consistingof 2,4-toluene diisocyanate and 2,6-toluene diisocyanate (TDI); mixturesof the two TDI isomers; 4,4′-diisocyanatodiphenylmethane (MDI);p-phenylene diisocyanate (PPDI); diphenyl-4,4′-diisocyanate;dibenzyl-4,4′-diisocyanate; stilbene-4,4′-diisocyanate;benzophenone-4,4′-diisocyanate; 1,3- and 1,4-xylene diisocyanates andmixtures thereof.
 12. The erosion resistant article of claim 1, whereinthe isocyanate-terminated prepolymer is made from diisocyanates selectedfrom the group consisting of 1,6-hexamethylene diisocyanate (HDI);1,3-cyclohexyl diisocyanate; 1,4-cyclohexyl diisocyanate (CHDI); thesaturated diphenylmethane diisocyanate H12MDI;bis{4-isocyanatocyclohexyl}methane, 4,4′-methylene dicyclohexyldiisocyanate, 4,4-methylene bis (dicyclohexyl)diisocyanate, methylenedicyclohexyl diisocyanate, methylene bis(4-cyclohexylene isocyanate),saturated methylene diphenyl diisocyanate, and saturated methyl diphenyldiisocyanate), isophorone diisocyanate (IPDI); hexamethylenediisocyanate (HDI), 2,2,4- and/or 2,4,4-trimethyl-1,6-hexamethylenediisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane,1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,4′-and/or 4,4′-diisocyanato-dicyclohexyl methane, 2,4- and/or4,4′-diisocyanato-diphenyl methane and mixtures of these isomers withtheir higher homologues which are obtained by the phosgenation ofaniline/formaldehyde condensates, 2,4- and/or 2,6-diisocyanatotolueneand mixtures of these compounds.
 13. The erosion resistant article ofclaim 1, wherein the isocyanate-terminated prepolymer is made fromdiisocyanates selected from the group consisting of hexamethylenediisocyanate (HDI), 2,2,4- and/or 2,4,4-trimethyl-1,6-hexamethylenediisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane,1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,4′-and/or 4,4′-diisocyanato-dicyclohexyl methane, 2,4- and/or4,4′-diisocyanato-diphenyl methane and mixtures of these isomers withtheir higher homologues which are obtained by the phosgenation ofaniline/formaldehyde condensates, 2,4- and/or 2,6-diisocyanatotolueneand any mixtures of these compounds.
 14. The erosion resistant articleof claim 1 wherein the curing agent is selected from the groupconsisting of 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, polyetherpolyol, polyester polyols, polycaprolactone polyols, polyether polyols,polyhydroxy polycarbonates, polyhydroxy polyacetals, polyhydroxypolyacrylates, polyhydroxy polyester amides, polyhydroxy polythioethersand mixtures thereof.
 15. The coating composition of claim 1, whereinthe isocyanate-terminated prepolymers are selected from the groupconsisting of TDI-ether, TDI-ester, TDI-lactone, MDI-ether, MDI-ester,H₁₂MDI-ether, H₁₂MDI-ester and prepolymers made from diisocyanatesselected from the group consisting of HDI, IPDI, and PPDI.
 16. Theerosion resistant article of claim 2 wherein the cured form comprises anadditional layer of primer or adhesive integral with said polyurethaneor polyurea coating forming a two layer structure which is adhesivelybonded to the airfoil substrate.
 17. The erosion resistant article ofclaim 16 wherein the cured form comprises an additional topcoat layerover said polyurethane or polyurea coating forming a three layer whichis adhesively bonded to the airfoil substrate.